Polymers and copolymers of acenaphthylene



Patented July l3,

POLYMERS AND COPOLYMEBS F ACENAPHTIIYLENE Harry I. Miller and Ralph o. Pittsileld, Mesa, assignorl to General Electric Company, a corporation of New York No 1mm. sppuesmn'sepumserzs, 1944,

Serial m. ssasss 7 Claims. (01. zoo-so) The present invention relates generally to the production of polymers and copolymers oi acenaphthylene. More specifically, the invention is concerned with the production of high molecular weight polymers of acenaphthylene and copolymers oi acenaphthylene with compounds contain; ing at least one polymerizable grouping.

Acenaphthylene, which is an unsaturated hydrocarbon of the formula has heretofore been polymerized to polymers of low molecular weight (Ber. 1914, 47, 1685) by heating the acenaphthylene in solution, a short chain polymer of average molecular weight oi the order oi 3200-3300 being obtained. In accordance with the present invention polymers of acenaphthylene are produced which have high molecular weight of the order of at least 150,000. These polymers have high softening points and can be utilized at elevated temperatures ior electrical insulation purposes.

Copolymers may also be produced in accord- I ance with the present invention by polymerizing aoenaphthylene with any compound containing at least one polymerizable grouping, illustrative examples oi which are:

others, vinyl esters, vinyl halides, vinyl phthalamide, acrylic acid. acrylic acid esters. methacrylic acid esters, acrylonitrile; unsaturated hydrocarbons such as isoprene, vinyl acetylene, butadien'e. isobutylene; propenyl methyl ketone; polymerizable aryl compounds having one or more unsaturated side chains such as p-methoxypropenyl benzene, propenyl benzene; o-hydroxy styrene, divinyl benzene. and isoeugenol. Indene and indene derivatives also may be copolymerized with acenaphthylene.

In order that those skilled in the art better may understand how the present invention may be carried into eflect, the following examples are given by way of illustration. All parts are by weight.

Example 1 A slow stream oi BF: gas was passed through an ether solution of acenaphthylene containing 8.9 parts of the hydrocarbon at C., the solution being allowed to warm up to 25 C. After standing four hours a precipitate formed. The polymer was reprecipitated from a benzene solution with methyl alcohol. Molecular weight determinations on the di'ilerent chain length iractions of the polymer showed values of 183,000 and 341,000. Molecular weight measurements were made by the Mead and Fuoss method described in Jour. Phys. Chem. vol. 47, No. 1, January 1943, pp. 59---'I0.-

Example 2 15 parts acenaphthylene in parts (by volume) chlorbenzene were cooled to approximately 0 C. and BF: gas bubbled slowly through the solution. A white powder was obtained on dilution of the chlorbenzene solution with methyl alcohol. This product did not i'low at 220 C. under a pressure 0! 30,000 pounds which is indicative of very high molecular weight polymers.

Example 3 31 parts of acenaphthylene in chlorbenzene solution were polymerized with a slow stream of B1": gas. The temperature was held below 0 C.

' for the reaction period (15 minutes) and a white 40' vinyl compounds such as vinyl carbazole, vinylproduct was obtained on dilution with methyl alcohol. This polymer was plasticized with Dowtherm A (diphenyl-diphenylene oxide eutectic mixture) and coated on 0.0004" plain krai't-paper. After two weeks in an 80 C. 'Oven the polyacenaphthylene coated paper still retained its original pliability.

' Example 4 37 parts of a very high molecular weight polymer were obtained by'polymerizing at -15 to 20 C., for 30 minutes, 50 parts of acenaphthylene in parts (by volume) chlorbenzene with a very slow current oi BF: gas. The polymer, which'was a white product. was plasticized with s-methylnaphthalene and coated on 0.0004" krait paper. A laminated product was made by pressing together at 180 C. and 20,000 pounds pressure '1 sheets of this polyacenaphthylene coated paper and used as the dielectric material in a capacitor. Measurements made on the capacitor showed an initial dielectric constant of 4.15 and power factors of 1.4% and 0.84% at 28 C. and .85 C. respectively. leakage resistances i. and 85' C. were. respectively, 2,390,000 ohms/c and 210,000 ohms/cm}.

. Example 5 99 parts polyacenaphthylene were mixed with 20 partspolystyrene and 20 parts of a-methyl naphthalene as plasticizer in 400 parts (by volume) oi trichloroethylene. The solution was used to coat 0.0004" kraft paper which was built up to 0.0012" with the resin The material was laminated by stacking six sheets and pressing at 150-160 C. and 15,000 pounds pressure. The resulting-product is a transparent sheet useful in making high frequency capacitors.

Example 8,

9 parts acenaphthylene and 29 parts oi vinyl carbazole were refluxed in benzene as a solvent and benzoyl peroxide as the catalyst for 48 hours in an oil bath at 100 C. The copolymer, twice Example 7 30 parts of vinyl carbazole were copolymerized with 5 parts of aeenaphthylene using benzoylperoxide as the catalyst and benzene as the solvent, by heating in an oil bath at 100 C. for several days. The product was precipitated {mm the benzene solution as a white powder which did not melt on the 200 0. hot plate.

Example 8 500 parts of vinyl carbazole and 155 parts of acenaphthylene were copolymerized using benzoyl peroxide as the catalyst and benzene (050 parts by volume) as the solvent by heating the mixture for 168 hours in an oil bath at 105 C. Theproduct, a white powder, was precipitated from the benzene solution, did not melt on the 200 C. hot plate, and was used to coat paper as described in Example 4.

Example 9 5 parts 01 acenaphthylene were copolymerized with 10 parts oi. styrene at about 0 C. using BF: gas for 30 minutes. This copolymer when coated on paper, possessed good laminating properties.

Example 10 1 1 part 01' acenaphthylene and 9 parts oi vinyl acetate were copolymerized at 100 C. with benzoyl peroxide as the catalyst and precipitated as a white powder with methyl alcohol.

1 Example 11 preparation of interpolymers of acenaphthylene and a compound containing a poiymerizable grouping wherein the acenaphthylene comprises from 10 to 33%, per cent, by weight, of the interpolymer. I

It will be understood by those skilled in the art that the invention is not limited to the production of copolymers of acenaphthylene with the particular compounds'given in the above illustrative examples. Any compound containing at least one polymerizable grouping, numerous examples or which have hereinbeiore been mentioned, may be used. In certain cases, instead or polymerizing a single organic compound containing a polymerizable grouping, the acenaphthyiene may be copolymerized with a plurality of compounds each containing at least one polymerizable grouping. Thus, it is possible to obtain compositions comprising a. mixture of interpolymers best adapted to meet particular service applications.

Although in the production of the copolymers illustrated in the i'oregoing examples, benzoyl peroxide and boron triiluoride have been indicated as polymerization catalysts. other suitable polymerization catalysts may be used. Benzoyl peroxide is usually the preferred catalyst for copolymerizations. Any suitable amount of catalyst may be used, but in general the catalyst concentration will be within the range of 0.1 to 1.0% by weight of the whole. The rate of polymerization and the properties or the final product vary with the time, temperature and with the catalyst and its concentration. Polymerizations may be eli'ected at various temperatures depending on the catalyst used.

The proportions oi monomeric constituents used in preparing the various copolymer products of the present invention are not restricted to the proportions given in the above examples. Various proportions of monomers may be used in preparing the copolymers, depending upon the type of copolymer desired and the use to which it is to be put.

The polymers and copolymers of the present invention may be used alone or with illlers, plasticizers or other modifying bodies compatibletherewith. As noted in the examples, the high molecular weight polymers of this invention, as well as thecopolymers, are adapted for use in coating paper and the like, for the production 01' laminated dielectric material for use in electrical devices, such as capacitors, the polymers and copolymers of the present invention being particularly adapted tor-use in high frequency electrical applications where high heat resistance is desired.

What we claim as new and desire to secure by Letters Patent 01' the United States is:

,1. A composition comprising the polymer of ingredients comprising acenaphthylene and styrene in the ratio of, by weight, 5 parts of the former to 10 parts of the latter.

2. A composition or matter comprising an interpolymer of a mixture of copolymerizable ina compound containing a polymerizable cal-=0 grouping, the said interpolymer containing from 10 to 33 V per cent, by weight, of acenaphthylene.

3. A composition of matter comprising an interpolymer of a mixture of copolymerizable ingredients comprising (1) acenaphthylene and (2) vinyl carbazole, the acenaphthylene comprising from 10 to 33 /3 per cent, byvweight, of the interpolymer.

4. A composition of matter comprising an interpolymer of a mixture of copolymerizable ingredients comprising (1) acenaphthy lene and (2) styrene, the acenaphthylene comprising from 10 to 33 per cent, by weight, of the interpolymer.

5. A composition of matter comprising an interpolymer of a mixture of copolymerizable ingredients comprising (1) acenaphthylene and (2) vinyl acetate, the acenaphthylene comprising from 10 to 33 per cent, by weight; of the interpolymer.

6. The process of preparing new synthetic compositions which comprises polymerizing a mixture containing (1) acenaphthylene and (2) a compound containing a polymerizable i OH1=O 1 grouping, the acenaphthylene comprising from 10 to 33% per cent, by weight, or the mixture or 'copolymerizable materials, the said polymerization being eflected in the presence of a. catalyst selected from the class consisting of BF: and benzoyl peroxide, said materials oi (1) and (2) being copolymerizable.

gradients comprising (1) acenaphthylene and (2) 7. They process oi preparing new synthetic compositions which comprises (1) forming a. mixture of ingredients in benzene comprising (1) acenaphthylene, (2) a compound containing a polymerizable CHFC/ grouping, and (3) benzoyl peroxide as a polyjo merization catalyst, the a'cenaphthylene being present in an amount equal to froiniO to 33 /3 per cent, by weight, of'the total weight of (,1) and (2), and thereafter heating the mixture'until copolymerization is obtained.

HARRY F. MILLER.

15' RALPH G. FLOWERS.

REFERENCES crrnn The following references are of record in the 0 file of this patent:

UNITED STATES PATENTS Number Name Date 2,114,233 Neher Apr. 12, 1938 5 2,317,878 Bannon Apr. 27, 1943 OTHER REFERENCES Beilstein, Handbuch der Organische Chemie,

'5 800., 58, 1051-2 (1936), abstracted in Chem. Abst.

X18111. Kurzes Hanbuch der Polymerisaticnsl chni vol. 11. page 45 (1941). 

